JPH03182725A - Non-linear optical element and manufacture thereof - Google Patents
Non-linear optical element and manufacture thereofInfo
- Publication number
- JPH03182725A JPH03182725A JP1317916A JP31791689A JPH03182725A JP H03182725 A JPH03182725 A JP H03182725A JP 1317916 A JP1317916 A JP 1317916A JP 31791689 A JP31791689 A JP 31791689A JP H03182725 A JPH03182725 A JP H03182725A
- Authority
- JP
- Japan
- Prior art keywords
- optical element
- nonlinear optical
- substrate
- thin film
- manufacturing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000003287 optical effect Effects 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000013078 crystal Substances 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 239000010409 thin film Substances 0.000 claims abstract description 25
- 238000009830 intercalation Methods 0.000 claims abstract description 4
- 230000002687 intercalation Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 17
- 239000004065 semiconductor Substances 0.000 claims description 12
- 238000004528 spin coating Methods 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000011368 organic material Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- -1 halogen ion Chemical group 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims 3
- 229910052793 cadmium Inorganic materials 0.000 claims 2
- 229910052802 copper Inorganic materials 0.000 claims 2
- 229910052748 manganese Inorganic materials 0.000 claims 2
- 239000013081 microcrystal Substances 0.000 claims 2
- 239000000853 adhesive Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 claims 1
- 239000002178 crystalline material Substances 0.000 claims 1
- 239000012044 organic layer Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- CDTCEQPLAWQMLB-UHFFFAOYSA-J tetraiodoplumbane Chemical compound I[Pb](I)(I)I CDTCEQPLAWQMLB-UHFFFAOYSA-J 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 102220587327 NEDD8-activating enzyme E1 catalytic subunit_H21N_mutation Human genes 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000001451 molecular beam epitaxy Methods 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002109 crystal growth method Methods 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- WPYVAWXEWQSOGY-UHFFFAOYSA-N indium antimonide Chemical compound [Sb]#[In] WPYVAWXEWQSOGY-UHFFFAOYSA-N 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 230000009022 nonlinear effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000000699 topical effect Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/3556—Semiconductor materials, e.g. quantum wells
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
Landscapes
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- General Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biophysics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Optical Integrated Circuits (AREA)
- Optical Modulation, Optical Deflection, Nonlinear Optics, Optical Demodulation, Optical Logic Elements (AREA)
Abstract
Description
【発明の詳細な説明】
Ａ、産業上の利用分野
本発明は光データ処理装置あるいは光通信に用いられ、
外部の光電気信号によって制御される光学素子に関する
。[Detailed Description of the Invention] A. Industrial Application Field The present invention is used in optical data processing devices or optical communications,
It relates to optical elements controlled by external opto-electrical signals.
Ｂ、従来技術及びその課題
第３次非線形光係数χは非線形光素子材料を評価するキ
ー・パラメータである。屈折率の実部及び虚数部はχが
十分に大きいときに顕著に光強度によって変化する。外
部の光あるいは電気によって制御される光素子は実用上
、大きなχ値を有する必要がある。B. Prior art and its problems The third-order nonlinear optical coefficient χ is a key parameter for evaluating nonlinear optical element materials. The real part and imaginary part of the refractive index change significantly depending on the light intensity when χ is sufficiently large. For practical purposes, optical elements controlled by external light or electricity need to have a large χ value.
半導体はよく知られるように大きなχを有するものがあ
り、半導体光素子との集積化の可能性を有している。As is well known, some semiconductors have a large χ and have the potential for integration with semiconductor optical devices.
これらの技術を示す文献としては以下のものがある。Documents showing these techniques include the following.
（１） Ｓ、Ｙ、 Ｙｕｅｎ ａｎｄ Ｐ、Ａ、 Ｗ
ｏｌｆｆ ：ＴｅｃｈｎｉｃａｌＤｉｇｅｓｔ ｐｐ
１５０−１５３ ｏｆ Ｎｏｎ１ｉｎｅａｒ ０ｐｔｉ
ｃａｌＰｒｏｐｅｒｔｉｅｓ ｏｆ Ｍａｔｅｒｉａｌ
ｓ Ｔｏｐｉｃａｌ Ｍｅｅｔｉｎｇ；Ａｕｇｕｓｔ、
１９８８．Ｔｒｏｙ、Ｎｅｗ ＹｏｒｋＤ、Ａ、Ｂ、Ｍ
ｉｌｌｅｒ、Ｃ，Ｔ、５ｅａｔｏｎ、Ｍ、Ｅ、Ｐｒ１ｃ
ｅａｎｄ Ｓ、Ｄ、Ｓｍ１ｔｈ ： Ｐｈｙｓ、Ｒｅｖ
、Ｌｅｔｔ、４７，１９７（１９８１）
Ｃ，に、Ｎ、 Ｐａｔｅｌ、 Ｒ，Ｅ、 ５ｌｕｓｈｅ
ｒ、 ａｎｄ、Ｐ、んＦｌｅ’ｕｒｙ：Ｐｈｙｓ、 Ｒ
ｅｖ、 Ｌｅｔｔ、 １７．１０１１−１０１７（１
９６６）Ｄ、Ａ、 Ｂ、 Ｍｉ １ｌｅｒ、 Ｄ、 Ｓ
、 Ｃｈｅｍｌａ、 Ｄ、Ｊ。(1) S, Y, Yuen and P, A, W
olff :Technical Digest pp
150-153 of Non1inear 0pti
calProperties of Material
s Topical Meeting; August,
1988. Troy, New York D, A, B, M
iller, C.T., 5eaton, M.E., Pr1c.
eand S, D, Sm1th: Phys, Rev
, Lett, 47, 197 (1981) C, N, Patel, R, E, 5rushe
r, and, P, Fle'ury: Phys, R
ev, Lett, 17.1011-1017(1
966) D, A, B, Mi 1ler, D, S
, Chemla, D.J.
Ｅｉｌｅｎｂｅｒｇｅｒ、Ｐ、Ｗ、Ｓｍ１ｔｈ、Ａ、Ｇ
、Ｇｏｓｓａｒｄａｎｄ Ｗ、Ｗｉｅｇｍａｎｎ ：
Ａｐｐｌ、Ｐｈｙｓ、Ｌｅｔｔ、。Eilenberger, P.W., Smlth, A.G.
, Gossardand W., Wiegmann:
Appl, Phys, Lett.
４２．９２５（１９８３）
Ｈ，Ｍ、Ｇｉｂｂｓ、Ｓ、Ｓ、Ｔａｒｎｇ、Ｊ、Ｌ、Ｊ
ｅｗｅｌｌ、Ｄ、Ａ。42.925 (1983) H.M., Gibbs, S.S., Tarng, J.L.J.
ewell, D.A.
Ｗｅｉｎｂｅｒｇｅｒ、ａｎｄ Ｋ、Ｔａｉ ： Ａ
ｐｐｌ、Ｐｈｙｓ、Ｌｅｔｔ、。Weinberger, and K., Tai: A.
ppl, Phys, Lett.
４１．２２１−２２２（１９８２）
Ａ、Ｈｏｎｏｌｄ、Ｌ、５ｃｈｕｌｔｈｅｉｓ、Ｊ、Ｋ
ｕｈｌ ａｎｄＣ，Ｗ、Ｔｕ ： Ｔｅｃｈｎｉ
ｃａｌ Ｄｉｇｅｓｔ ｏｆ １６ｔｈＩｎｔｅｒ
ｎａｔｊｏｎａｌ Ｃｏｎｆ、ｏｎ Ｑｕａｎｔｕｍ
Ｅｌｅｃｔｒｏｎｉｃｓ、 Ｔｏｋｙｏ、 （１９８８
）Ｔ、 ｌ５ｈｉｈａｒａ、 Ｊ、 Ｔａｋａｈａｇｈ
ｉ ａｎｄ Ｔ、Ｇｏｔｏ ：５ｏｌｉｄ ５ｔａｔ
ｅ Ｃｏｍｍｕｎｉｃａｔｉｏｎ、 ６９．９３３（１
９８９）（８） Ｅ、Ｈａｎａｍｕｒａ ： Ｎａｔ
ｏ ｗｏｒｋｓｈｏｐ ｏｎ″ＯｐｔｉｃａｌＳｗｉｔ
ｃｈｉｎｇ ｉｎ Ｌｏｗ−ｄｉｍｅｎｓｉｏｎａｌ
Ｓｙｓｔｅｍｓ 。41.221-222 (1982) A., Honold, L., 5chultheis, J.K.
uhl and C, W, Tu: Techni
cal Digest of 16thInter
Natjonal Conf, on Quantum
Electronics, Tokyo, (1988
) T, l5hihara, J, Takahagh
i and T, Goto: 5olid 5tat
eCommunication, 69.933(1
989) (8) E, Hanamura: Nat
o workshop on”OpticalSwit
Ching in Low-dimensional
Systems.
０ｃｔｏｂｅｒ、 （１９８８）、 Ｍａｒｂａｌｌａ
、 ５ｐａｉｎ（９） Ｙｕ、１．Ｄｏｌｚｈｅｎｋ
ｏ、 Ｔ、 Ｉｎａｂａ ａｎｄ Ｙ、 Ｍａｒｕｙａ
ｍａ ：Ｂｕｌｌ、 Ｃｈｕｍ、 Ｓｏｃ、Ｊａｐａｎ
、 ５９．５６３． （１９８６）狭いバンド・ギャッ
プを有する半導体はバンド・フィリング効果（参照文献
２）及び伝導帯（参照文献３）の非放物線形がきわめて
大きな非線形（例えばＩｎＳｂ単結晶に釦いて＝３Ｘ１
０ ’ｅａｕ）を引き起こす。しかし、この半導体で
は長波長域（５〜１０μｍ）にかいてのみ非線形効果が
大きく、光データ処理分野等で実用的に使用することが
できない。0ctober, (1988), Marballa
, 5pain(9) Yu, 1. Dolzhenk
o, T, Inaba and Y, Maruya
ma: Bull, Chum, Soc, Japan
, 59.563. (1986) Semiconductors with a narrow band gap have band filling effects (Ref. 2) and conduction bands (Ref. 3) with extremely large non-parabolic shapes (for example, in InSb single crystals = 3×1
0 'eau). However, this semiconductor has a large nonlinear effect only in the long wavelength range (5 to 10 μm), and cannot be used practically in the field of optical data processing.
光学素子の高いバッキング密度の達成のために、より短
波長域での大きなχ値を達成するメカニズムが望まれる
。半導体量子井戸における励起子の示す非線形性は最も
期待されるものである（参照文献４．５）。大きなχ値
は励起子吸収における吸収飽和により生じる。励起子遷
移における効果はバンド・ギャップが、広いときに（バ
ンド相互間遷移に比較して）よシ大きいため、このメカ
ニズムはよう短波長領域で効果的なものとなる。大きな
χ値を得るプロセスはバルク結晶のみならず、超格子構
造または量子井戸構造（以下、超格子構造体も含む意味
で用いる。）にかける励起子遷移の量子閉じ込め効果に
よるエンハンスメント効果があるため、−層効果的なも
のとなる。In order to achieve a high backing density in an optical element, a mechanism that achieves a large χ value in a shorter wavelength region is desired. The nonlinearity exhibited by excitons in semiconductor quantum wells is the most promising (Reference 4.5). The large χ value is caused by absorption saturation in exciton absorption. Since the effect on exciton transitions is larger when the band gap is wide (compared to interband transitions), this mechanism is effective at very short wavelengths. The process of obtaining a large χ value has an enhancement effect due to the quantum confinement effect of exciton transitions applied not only to bulk crystals but also to superlattice structures or quantum well structures (hereinafter used to include superlattice structures). - Become layer effective.
しかしながら、バルク結晶に比較して、量子井戸構造は
よう良好な特性を示すが、現実にはまだ以下のようない
くつかの問題点を有する。However, although the quantum well structure exhibits good properties compared to bulk crystals, it still has some problems in reality, as described below.
１）量子井戸における励起結合エネルギが低い（約１０
ｍｅＶ）ため、室温に釦けるフォノンが励起子数を減少
させてしまう。そのためにデバイスの動作はよシ強い吸
収を得るために液体窒素温度よりも下で行う必要がある
。1) The excitation coupling energy in the quantum well is low (approximately 10
meV), the phonons that warm up to room temperature reduce the number of excitons. Therefore, the device must be operated below liquid nitrogen temperature to obtain a strong absorption.
２）自由キャリアが長寿命であるためシステムの応答時
間が長くなシ、高速のデバイスが得にくい。2) Since the free carriers have a long lifetime, the response time of the system is long, making it difficult to obtain high-speed devices.
３）半導体量子井戸の製造には高価な設備及び複雑な製
造工程を必要とする（ＭＢＥ：分子線エピタキシ法、Ｍ
ＯＣＶＤ：有機金属化学気相堆積法、他）。3) Manufacturing semiconductor quantum wells requires expensive equipment and complicated manufacturing processes (MBE: molecular beam epitaxy, M
OCVD: metal organic chemical vapor deposition, etc.).
さらに、原子レベルまで完全にフラットな構造を有する
理想的な量子井戸構造を製造することは、今なか困難で
ある。エピタキシャル成長過程における不均一性が量子
井戸のサイズの不均一性を構成する。理想的な量子井戸
の場合の励起子の寿命は理論的な予測では２．８ｐａで
あるが、実際の構造では１８０ｐａとなってしまう（参
照文献６）。Furthermore, it is still difficult to manufacture an ideal quantum well structure having a completely flat structure down to the atomic level. Non-uniformity in the epitaxial growth process constitutes non-uniformity in quantum well size. The lifetime of an exciton in an ideal quantum well is theoretically predicted to be 2.8 pa, but in an actual structure it is 180 pa (Reference document 6).
応答が速く、かつ大きなχ値を得るためには、井戸構造
中に不均一性の存在しない半導体の量子井戸構造を得る
必要がある。この要請から半導体層と有機材料層とをイ
ンターカレーションさせた２次元ペロプスカイト型半導
体結晶（Ｃ１０Ｈ２１Ｎ Ｈ３） ２ Ｐ ｂ Ｉ ４
が注目されている。この（Ｃ１゜Ｈ２１ＮＨ３）２Ｐｂ
Ｉ４の結晶構造を第６図に示２＋
す。この図に示すとと（Ｐｂ と■とから構成サレ
ル単一量子井戸層がアルキルアンモニウムの２つの層に
挾まれた構成となっている。Ｐｂ２＋イオンに隣接した
Ｎ原子が配位子場を形成し、Ｐｂ２＋の光学遷移の波長
を決定する。これまで述べてきたことは半導体及び有機
材料のインターカレーションによる理想的な量子井戸構
造であり１井戸の厚みは結晶中全域にわた。り６．２４
Ａという一定の値を持つ。また、この量子井戸にかける
励起子結合エネルギは極めて大きく、観察された値によ
れば３７０ｍＶ（これはバルク結晶Ｐ ｂ Ｉ ２の約
１２倍である）となり１これによって第９図（、）に示
すように室温に訃いても十分な励起子の吸収ピークが得
られた。In order to obtain a fast response and a large χ value, it is necessary to obtain a semiconductor quantum well structure in which there is no non-uniformity in the well structure. In response to this request, a two-dimensional perovskite semiconductor crystal (C10H21N H3) 2 P b I 4 was created by intercalating a semiconductor layer and an organic material layer.
is attracting attention. This (C1゜H21NH3)2Pb
The crystal structure of I4 is shown in Figure 6. As shown in this figure, a Sarel single quantum well layer composed of Pb and ■ is sandwiched between two layers of alkylammonium.N atoms adjacent to Pb2+ ions form a ligand field. Then, determine the wavelength of the optical transition of Pb2+.What has been described so far is an ideal quantum well structure formed by intercalation of a semiconductor and an organic material, and the thickness of one well extends throughout the entire crystal.6. 24
It has a constant value of A. In addition, the exciton binding energy applied to this quantum well is extremely large, and according to the observed value, it is 370 mV (which is about 12 times that of the bulk crystal P b I 2 )1. As shown, sufficient exciton absorption peaks were obtained even at room temperature.
２次元ペロプスカイト型半導体結晶は非線形光学素子と
して極めて有効であると考えられる。しかし、実際の装
置に組みこむデバイスとして使用するのに十分な大きさ
を有する素子を結晶成長法（参照文献９）によって製造
するのは極めて困難である。シリカ溶融法によってｓ
２ Ｘ ２ Ｘ Ｏ−１ｍ ｍ ３の単結晶を得るには
１乃至２力月を要する。さらに、この方法は結晶サイズ
（特に結晶厚み）をコントロールするのが非常に難しい
。Two-dimensional perovskite semiconductor crystals are considered to be extremely effective as nonlinear optical elements. However, it is extremely difficult to manufacture an element having a size sufficient to be used as a device incorporated into an actual device by a crystal growth method (Reference Document 9). s by silica melting method
It takes 1 to 2 months to obtain a single crystal of 2 x 2 x O-1 m m 3 . Furthermore, this method makes it very difficult to control crystal size (especially crystal thickness).
Ｃ０発明の概要および解決課題
本発明は透明基板の上に２次元ペロプスカイト薄膜を作
成する新規なエピタキシャル技術を提供するものである
。これは非線形光学データ処理デバイスを実現するため
の基盤技術となシ得るものである。すなわち、高い光学
的品質を保ち、極めて速い応答性能と良好な非線形光学
性能を有する非線形光学素子を提供する。C0 Overview of the Invention and Problems to be Solved The present invention provides a novel epitaxial technique for creating a two-dimensional perovskite thin film on a transparent substrate. This can serve as a fundamental technology for realizing nonlinear optical data processing devices. That is, the present invention provides a nonlinear optical element that maintains high optical quality, has extremely fast response performance, and has good nonlinear optical performance.
Ｄ、実施例
実施例１
（ａ） （ｃｌ ０Ｈ２１ＮＨ３）２ＰｂＩ ４の合
成フラスコ内の１５０ｍ１蒸留水中に９．５ｇの鉛アセ
テートを混入する。氷酢酸２．８６ ｍ ｌ を攪拌し
ながら加える。１０ｍ１ のデシル・アミンを加え、１
０分間攪拌する。この溶液に１６．６ｇのヨウ化カリウ
ムを溶解した１００ｍ１の蒸留水を攪拌しながら加える
。厚みのあるオレンジ色のサスペンションをフィルタで
除去し、水洗する。得られた結晶を真空下で乾燥する。D. Examples Example 1 (a) Synthesis of (cl 0H21NH3)2PbI4 Mix 9.5 g of lead acetate in 150 ml of distilled water in a flask. 2.86 ml of glacial acetic acid are added with stirring. Add 10ml of decyl amine,
Stir for 0 minutes. 100 ml of distilled water in which 16.6 g of potassium iodide has been dissolved is added to this solution with stirring. Remove the thick orange suspension with a filter and wash with water. The crystals obtained are dried under vacuum.
生成物をニトロメタン中で金色の薄板状に再結晶する。The product is recrystallized in nitromethane to give golden platelets.
（ｂ） （Ｃ１０ Ｈ２１Ｎ Ｈ３） ２ Ｐ ｂ
Ｉ ４のスピン・コーティング
アセトンに５ ｗ ｔ ９６の（Ｃ１０Ｈ２１ＮＨ３）
２ＰｂＩ４ を溶解した溶液を、直径１インチの石英基
板（第１図、１）上にスピンコートする。スピン・スピ
ードは２０００ｒｐｍ とする。(b) (C10 H21N H3) 2 P b
Spin coating of I4 in acetone with 5 wt 96 (C10H21NH3)
A solution containing 2PbI4 is spin coated onto a 1 inch diameter quartz substrate (FIG. 1, 1). The spin speed is 2000 rpm.
（ｃ）生成膜の評価
第１図に示すごとく、基板１の上に（Ｃ１０Ｈ２１Ｎ
Ｈ３） ２ Ｐ ｂ Ｉ４薄膜２が形成される。生成膜
の厚さ、及び平滑さは、ＷＹＫＯ干渉装置によって計測
した。結果を第７図に示す。基板のエツジ部を除いて、
１１００ｎ厚、凹凸がλ／１００以下のオプティカル・
フラットな薄膜が得られた。(c) Evaluation of produced film As shown in Figure 1, (C10H21N
H3) 2 P b I4 thin film 2 is formed. The thickness and smoothness of the produced film were measured using a WYKO interferometer. The results are shown in FIG. Except for the edge of the board,
Optical with a thickness of 1100n and unevenness of less than λ/100.
A flat thin film was obtained.
Ｘ線回折法によって薄膜の結晶構造評価を行った。第８
図にＸ線回折角度に対するＸ線回折強度分布を示す。図
から結晶は２１．３ Ａの明確な周期を有していること
がわかる。これは第６図に示すごとく、結晶中Ｃ軸方向
に沿ってｐｂの２次元層が２１．３Ａの間隔で存在して
いることを示すものである。この結果ｂｐｂＩ４の各層
、すなわち量子井戸が２１．２５Ａごとに存在するいわ
ゆる多重量子井戸構造が基板表面上に形成されたことが
分かる。結晶のａ軸、及びｂ軸方向の規則性はＸ線回折
においては検知できなかった。しかし、（Ｃ１０Ｈ２１
ＮＨ３）２ＰｂＩ４単結晶そのものの場合でも量子閉じ
込め効果はＣ軸方向の構造にのみ依存するものであり、
このようなＣ軸方向にのみ量子井戸構造を有するケース
に釦いても量子閉じ込め効果に基づく光学的効果は十分
なものが得られる。The crystal structure of the thin film was evaluated by X-ray diffraction method. 8th
The figure shows the X-ray diffraction intensity distribution with respect to the X-ray diffraction angle. It can be seen from the figure that the crystal has a well-defined period of 21.3 A. As shown in FIG. 6, this indicates that two-dimensional layers of pb exist at intervals of 21.3A along the C-axis direction in the crystal. As a result, it can be seen that a so-called multiple quantum well structure in which each layer of bpbI4, that is, a quantum well exists every 21.25 A, was formed on the substrate surface. Regularity in the a-axis and b-axis directions of the crystal could not be detected by X-ray diffraction. However, (C10H21
Even in the case of the NH3)2PbI4 single crystal itself, the quantum confinement effect depends only on the structure in the C-axis direction,
Even in such a case where the quantum well structure is provided only in the C-axis direction, sufficient optical effects based on the quantum confinement effect can be obtained.
薄膜（５％溶液から生成）の吸収スペクトルを第９図（
ｂ）に示す。ＰｂＩ４量子井戸の励起子吸収を示す２．
４２ｅＶ付近での強い吸収ピークが単結晶の場合（第９
図（ａ））と同様に観察された。The absorption spectrum of the thin film (produced from a 5% solution) is shown in Figure 9 (
Shown in b). 2. Showing exciton absorption in PbI4 quantum well.
In the case of a single crystal, a strong absorption peak near 42 eV (9th
Observations were made in the same manner as in Figure (a)).
顕微鏡観察によれば、この薄膜中には観察可能なりリス
タル・ドメインは存在しなかった。一方、１０ｗｔ％（
Ｃ１０Ｈ２１ＮＨ３）２ＰｂＩ４溶液を使用したスピン
コーティングにおいては、薄膜は不透明となり、多くの
結晶粒界が観察された。According to microscopic observation, there were no observable listal domains in this thin film. On the other hand, 10 wt% (
Upon spin coating using C10H21NH3)2PbI4 solution, the thin film became opaque and many grain boundaries were observed.
従来の方法に従えば、例えば最□も大きい部類に属する
２ Ｘ ２ Ｘ Ｏ，１ｍｍ３の単結晶を成長させるに
は数カ月を要する。しかし、本発明で提示する技術に従
えば、半日程度で生成可能な粉末結晶を用いて、基板上
に大面積を有し、良好な光学的性能を備えた薄膜結晶を
スピンコートにより、たちどころに形成することができ
る。スピンコートによるこのような性質を有する薄膜の
形成技術は、従来行なわれてきたＭＢＥ法やＭＯＣＶＤ
法のような複雑でかつ高価な設備、及び高度な技術が要
求される製法に代わジ得る技術となう得るものである。According to the conventional method, it takes several months to grow, for example, a single crystal of 2 x 2 x O, 1 mm3, which belongs to the largest category. However, according to the technology presented in the present invention, using powder crystals that can be produced in about half a day, a thin film crystal with a large area and good optical performance can be quickly formed on a substrate by spin coating. can be formed into The technology for forming thin films with these properties by spin coating is similar to the conventional MBE method and MOCVD.
This technology can replace manufacturing methods that require complicated and expensive equipment and advanced technology, such as manufacturing methods.
な訃、溶剤はアセトンに限らずデイメトキシン・エタン
等、（ｃ １０ Ｈ２１Ｎ Ｈｓ ） ２ Ｐ ｂ Ｉ
４に対して適当な溶剤が選択可能である。The solvent is not limited to acetone, but also dimethoxine, ethane, etc. (c 10 H21N Hs ) 2 P b I
A suitable solvent can be selected for 4.
実施例２
第１実施例と異なる構造を第２図に示す。第１実施例と
の差異は導波路層３の存在である。当実施例では、石英
基板上にまず１μｍのコーニング７０５９ガラス層がス
パッタされる。次に、第１実施例と同様スピンコートに
よって２００ ｎｍの（ＣＨＮＨ） ｐｂＩ４層２を
形成する。Embodiment 2 A structure different from that of the first embodiment is shown in FIG. The difference from the first embodiment is the presence of the waveguide layer 3. In this example, a 1 μm layer of Corning 7059 glass is first sputtered onto a quartz substrate. Next, a 200 nm thick (CHNH)pbI4 layer 2 is formed by spin coating as in the first embodiment.
０２１３２
これによって薄膜層及び７０５９ガラス層に沿った２、
４ ｅ Ｖのエネルギーを有するフォトンを光導波路
に入射する。導波モード励起のためにプリズム・カップ
ラ法を用いた。２ｐｓのパルス幅を有する２、 ４ ｅ
Ｖの光を基板に垂直な方向から照射すると、もともと
導波層を通っていた２、 ４ ｅ Ｖのエネルギーを持
つ光ビームの強度は２７倍に増加される。この光による
光学偏調は（Ｃ１０Ｈ２ｊＮＨ３）２Ｐ ｂ Ｉ ４に
かける高速応答特性を示している。02132 This results in 2 along the thin film layer and the 7059 glass layer.
Photons with an energy of 4 eV are incident on the optical waveguide. A prism coupler method was used for waveguide mode excitation. 2, 4 e with a pulse width of 2 ps
When the substrate is irradiated with light of V from a direction perpendicular to the substrate, the intensity of the light beam having an energy of 2.4 e V, which originally passed through the waveguide layer, is increased by 27 times. Optical polarization by this light shows a high-speed response characteristic applied to (C10H2jNH3)2P b I 4 .
実施例３
本実施例では（ＣＩ Ｄ Ｈ２１Ｎ Ｈ３） ２ Ｐ
ｂ Ｉ ４とリソグラフィのためのレジストとの多重層
が形成される。第３図に示すごとく（Ｃ１０Ｈ２□Ｎ
Ｈ３） ２ＰｂＩ４層４とポリ（ジーｎ−へキシルシラ
ン）層５から構成される。これらの各々の層は１１００
ｎから３ＤＯｎｍの厚みを有する（Ｃ１ＤＨ２１Ｎ Ｈ
３） ２ Ｐ ｂ Ｉ ４のスピンコーティングは第１
実施例と同様の方法で行なわれる。高分子ポリ（ジ−ｎ
−ヘキシルシラン）層５はイソオクタンを溶媒とした２
、５９６溶液のスピンコーティングによつて形成される
。Example 3 In this example, (CI D H21N H3) 2 P
A multilayer of b I 4 and resist for lithography is formed. As shown in Figure 3 (C10H2□N
H3) Consists of a 2PbI4 layer 4 and a poly(d-n-hexylsilane) layer 5. Each of these layers has 1100
(C1DH21N H
3) Spin coating of 2 P b I 4 is the first
It is carried out in the same manner as in the examples. High molecular weight poly(di-n)
-hexylsilane) layer 5 is 2 using isooctane as a solvent.
, 596 solution by spin coating.
この構造体を用いて光変調実験を行った。入射ビーム及
び制御ビームの波長は第２実施例と同様である。本実施
例では入射光は基板に垂直入射する平行光であう、入射
角１５°の制御光ビームに因って制御される。入射画像
情報の光による情報処理は入射光ビーム・アレイの反対
方向に配置したＣＣＤカメラで観測した。Light modulation experiments were conducted using this structure. The wavelengths of the incident beam and control beam are the same as in the second embodiment. In this embodiment, the incident light is controlled by a control light beam having an incident angle of 15°, which is parallel light that is perpendicularly incident on the substrate. Information processing of incident image information by light was observed with a CCD camera placed in the opposite direction of the incident light beam array.
実施例４
第４図に示すように半透明鏡６を有する石英基板１をス
ピンコート用の基板として使用した。第１実施例と同様
（Ｃ１０Ｈ２１ＮＨ３）２Ｐｂ工。層が形成される。次
に、この層の上に半透明鏡７として金が蒸着される。こ
の２つの半透明鏡は光共振器として作用する。２．４５
ｅ Ｖのエネルギーを持った光ビームを基板へ垂直入
射する。共振器を通過した光は第１０図に示すような双
安定特性を有している。Example 4 As shown in FIG. 4, a quartz substrate 1 having a semi-transparent mirror 6 was used as a substrate for spin coating. Same as the first example (C10H21NH3)2Pb process. A layer is formed. Gold is then evaporated onto this layer as a semi-transparent mirror 7. These two semi-transparent mirrors act as optical resonators. 2.45
A light beam with an energy of e V is vertically incident on the substrate. The light passing through the resonator has bistable characteristics as shown in FIG.
実施例５
他の２次元ペロブスカイト型ＭＸ４（ＣｎＨ２ｎ＋１Ｎ
ｕ ３ ） ２ を合成し薄膜として使用した。ここ
でＭは金属イオン：Ｃｕ、ＣｄｌＭｎ％Ｇｅ及びＦｅイ
オン、Ｘはハロゲンイオン二Ｉ％Ｃｌ、及びＢｒイオン
を表す。モノ・アンモニウムであるアルキル・アンモニ
ウム： ｎ＝３．５％ ８、又は１０を使用した。これ
らのペロブスカイトにおいてもスピンコート薄膜層にお
いて、量子井戸構造の周期性を見い出した。Example 5 Another two-dimensional perovskite type MX4 (CnH2n+1N
U 3 ) 2 was synthesized and used as a thin film. Here, M represents metal ions: Cu, CdlMn%Ge and Fe ions, and X represents halogen ions, I%Cl, and Br ions. Mono-ammonium alkyl ammonium: n=3.5% 8 or 10 was used. We also found periodicity in the quantum well structure in the spin-coated thin film layer of these perovskites.
実施例６
２次元ペロブスカイトとして（Ｃ５Ｈ１１ＮＨ３）２Ｐ
ｂＩ。を用いた第４実施例に類似した構成を第５図に示
す。第４実施例と同様、金の半透明鏡８を形成した石英
ディスクが基板として用いられる。Example 6 (C5H11NH3)2P as a two-dimensional perovskite
bI. FIG. 5 shows a configuration similar to the fourth embodiment using . As in the fourth embodiment, a quartz disk on which a gold semitransparent mirror 8 is formed is used as the substrate.
しかし本実施例では、薄膜９は基板１の金属層側に形成
される。さらにこの表面に半透明鏡１０が形成される。However, in this embodiment, the thin film 9 is formed on the metal layer side of the substrate 1. Furthermore, a semi-transparent mirror 10 is formed on this surface.
この実施例においても第４実施例（第１１図）と同様の
双安定特性が得られた。In this example as well, the same bistable characteristics as in the fourth example (FIG. 11) were obtained.
Ｅ１発明の効果
上述のごとく本発明によれば、複雑でかつ時間を要する
単結晶製造工程を経ずに量子井戸構造を構成することが
可能となシ、低コストで、かつ簡易な工程で非線形光学
素子を得ることができる。E1 Effects of the Invention As described above, according to the present invention, it is possible to construct a quantum well structure without going through the complicated and time-consuming single crystal manufacturing process, and it is possible to construct a quantum well structure at low cost and with a simple process. An optical element can be obtained.
第１図、第２図、第３図、第４図、第５図は各々本発明
の光学素子の異なる実施例の構成を示す断面図、第６図
は本発明で用いた（Ｃ５Ｈ１，ＮＨ３）２ＰｂＩ４の単
結晶構造を示す結晶構造図、第７図は生成膜のＷＹＫＯ
干渉装置による測定結果を示す図、第８図は生成膜のＸ
線回折図、第９図は本発明による薄膜と単結晶釜々の吸
収スペクトルを示す図、第１０図、及び第１１図はそれ
ぞれ本発明の異なる実施例の薄膜の双安定特性図である
。
１・・・・基板、２．４．９・・・・有機材料薄膜、３
・・・・ガラス層、５・・・・レジスト層、６．７．８
．１０・・・・半透明鏡
第１図
第２図
第３図
第４図
第５図
第６図
第７図
×回
電子エキル千１ｅＶｌ
ＩＮ９図
第１０図
第１１区
入力強度（イｆ、！目盛）
入力強度（任意目金）1, 2, 3, 4, and 5 are cross-sectional views showing the configurations of different embodiments of the optical element of the present invention, and FIG. ) A crystal structure diagram showing the single crystal structure of 2PbI4, Figure 7 shows the WYKO of the produced film.
A diagram showing the measurement results by the interference device, Figure 8 shows the X of the produced film.
A line diffraction diagram, FIG. 9 is a diagram showing absorption spectra of a thin film according to the present invention and a single crystal pot, and FIGS. 10 and 11 are bistable characteristic diagrams of thin films of different embodiments of the present invention. 1...Substrate, 2.4.9...Organic material thin film, 3
...Glass layer, 5...Resist layer, 6.7.8
．． 10... Semi-transparent mirror Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 scale) Input strength (arbitrary scale)
Claims (1)
薄膜構造体であり、該薄膜構造体は互いにエネルギー・
ギャップの異なる半導体層と有機質層とからなるインタ
ーカレーシヨン構成による微細構造を上記基板に対して
垂直な方向に有しており、該微細構造は超格子構造であ
ることを特徴とする非線形光学素子。 （２）上記薄膜構造体は、該構造体に入射される入射光
の波長よりも短い結晶軸のみから構成される微細結晶の
集合であり、該微細結晶の各々は上記基板に対して垂直
な方向に結晶軸の所定軸を有し、上記基板に対して平行
な方向には各々ランダムに結晶軸を有する結晶であるこ
とを特徴とする特許請求の範囲第１項記載の非線形光学
素子。 （？）上記薄膜構造体は（Ｃ＿１＿０Ｈ＿２＿１ＮＨ＿
３）＿２ＰｂＩ＿４から成ることを特徴とする特許請求
の範囲第１項又は第２項記載の非線形光学素子。 （４）上記薄膜構造体はＭＸ＿４（Ｃ＿ｎＨ＿２＿ｎ＿
＋＿１ＮＨ＿３）＿２（ただし、Ｍは金属イオンであつ
て、Ｃｕ、Ｃｄ、Ｍｎ、Ｇｅ、Ｆｅイオンのいずれかを
表わし、Ｘはハロゲン・イオンであつて、Ｉ、Ｃｌ、Ｂ
ｒイオンのいずれかを表わす） から成ることを特徴とする特許請求の範囲第１項又は第
２項記載の非線形光学素子。 （５）有機質材料を溶剤に溶解させ、該溶液を基板に対
してスピンコートすることにより、該基板に対して垂直
な方向に結晶軸の１軸を有し、該方向にエネルギ・ギャ
ップの異なる２種類の層が交互に積層する超格子構造を
持つ有機質材料薄膜を形成することを特徴とする非線形
光学素子の製造方法。 （６）上記有機質材料は（Ｃ＿１＿０Ｈ＿２＿１ＮＨ＿
３）＿２ＰｂＩ＿４から成ることを特徴とする特許請求
の範囲第５項記載の非線形光学素子の製造方法。 （７）上記有機質材料はＭＸ＿４（Ｃ＿ｎＨ＿２＿ｎ＿
＋＿１ＮＨ＿３）＿２（ただし、Ｍは金属イオンであつ
て、Ｃｕ、Ｃｄ、Ｍｎ、Ｇｅ、Ｆｅイオンのいずれかを
表わし、Ｘはハロゲンイオンであつて、Ｉ、Ｃｌ、Ｂｒ
イオンのいずれかを表わす） から成ることを特徴とする特許請求の範囲第５項記載の
非線形光学素子の製造方法。 （８）上記溶剤はアセトンであることを特徴とする特許
請求の範囲第５項乃至第７項のいずれかに記載の非線形
光学素子の製造方法。 （９）上記溶剤はデイメトキシン・エタンであることを
特徴とする特許請求の範囲第５項乃至第７項のいずれか
に記載の非線形光学素子の製造方法。 （１０）（Ｃ＿１＿０Ｈ＿２＿１ＮＨ＿３）＿２ＰｂＩ
＿４をアセトンに溶解させ、１０ｗｔ％未満の濃度の（
Ｃ＿１＿０Ｈ＿２＿１ＮＨ＿３）＿２ＰｂＩ＿４溶液を
作成し、該溶液を基板上に２０００ｒｐｍ以上のスピン
・スピードでスピンコートすることにより、基板に対し
て垂直な方向に結晶軸の１軸を有し、該方向にエネルギ
・ギャップの異なる２種類の層が交互に積層する超格子
構造を持つ（Ｃ＿１＿０Ｈ＿２＿１ＮＨ＿３）＿２Ｐｂ
Ｉ＿４薄膜を形成することを特徴とする非線形光学素子
の製造方法。[Scope of Claims] (1) A thin film structure adhered to a substrate without using an adhesive, and the thin film structure mutually absorbs energy.
A nonlinear optical element having a fine structure with an intercalation structure consisting of a semiconductor layer and an organic layer with different gaps in a direction perpendicular to the substrate, and the fine structure having a superlattice structure. . (2) The thin film structure is a collection of microcrystals consisting only of crystal axes shorter than the wavelength of the incident light incident on the structure, and each of the microcrystals is perpendicular to the substrate. 2. The nonlinear optical element according to claim 1, wherein the nonlinear optical element is a crystal having a predetermined crystal axis in a direction and having crystal axes randomly in a direction parallel to the substrate. (?) The above thin film structure is (C_1_0H_2_1NH_
3) The nonlinear optical element according to claim 1 or 2, characterized in that it is made of_2PbI_4. (4) The above thin film structure is MX_4 (C_nH_2_n_
+_1NH_3)_2 (where M is a metal ion and represents one of Cu, Cd, Mn, Ge, or Fe ions, and X is a halogen ion and represents I, Cl, or B
3. The nonlinear optical element according to claim 1 or 2, characterized in that the nonlinear optical element is made of: (5) By dissolving an organic material in a solvent and spin-coating the solution onto a substrate, a crystalline material with one crystal axis in a direction perpendicular to the substrate and with a different energy gap in this direction can be obtained. A method for manufacturing a nonlinear optical element, comprising forming an organic material thin film having a superlattice structure in which two types of layers are alternately laminated. (6) The above organic material is (C_1_0H_2_1NH_
3) The method for manufacturing a nonlinear optical element according to claim 5, characterized in that the nonlinear optical element is made of_2PbI_4. (7) The above organic material is MX_4 (C_nH_2_n_
+_1NH_3)_2 (However, M is a metal ion and represents either Cu, Cd, Mn, Ge, or Fe ion, and X is a halogen ion and represents I, Cl, or Br.
The method for manufacturing a nonlinear optical element according to claim 5, characterized in that the nonlinear optical element is made of: (8) The method for manufacturing a nonlinear optical element according to any one of claims 5 to 7, wherein the solvent is acetone. (9) The method for manufacturing a nonlinear optical element according to any one of claims 5 to 7, wherein the solvent is dimethoxine ethane. (10) (C_1_0H_2_1NH_3)_2PbI
_4 was dissolved in acetone and a concentration of less than 10 wt% (
By creating a C_1_0H_2_1NH_3)_2PbI_4 solution and spin-coating the solution onto a substrate at a spin speed of 2000 rpm or more, one crystal axis is perpendicular to the substrate and an energy gap is created in this direction. (C_1_0H_2_1NH_3)_2Pb has a superlattice structure in which two types of layers with different values are stacked alternately.
A method for manufacturing a nonlinear optical element, characterized by forming an I_4 thin film.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1317916A JPH03182725A (en) | 1989-12-08 | 1989-12-08 | Non-linear optical element and manufacture thereof |
| EP90313351A EP0431973B1 (en) | 1989-12-08 | 1990-12-07 | Nonlinear optical device and method of manufacturing |
| DE69025564T DE69025564T2 (en) | 1989-12-08 | 1990-12-07 | Nonlinear optical devices and manufacturing processes |
| US07/939,965 US5547705A (en) | 1989-12-08 | 1992-09-04 | Nonlinear optical device and method of manufacturing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1317916A JPH03182725A (en) | 1989-12-08 | 1989-12-08 | Non-linear optical element and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03182725A true JPH03182725A (en) | 1991-08-08 |
Family
ID=18093479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1317916A Pending JPH03182725A (en) | 1989-12-08 | 1989-12-08 | Non-linear optical element and manufacture thereof |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5547705A (en) |
| EP (1) | EP0431973B1 (en) |
| JP (1) | JPH03182725A (en) |
| DE (1) | DE69025564T2 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6700550B2 (en) | 1997-01-16 | 2004-03-02 | Ambit Corporation | Optical antenna array for harmonic generation, mixing and signal amplification |
| US6038060A (en) * | 1997-01-16 | 2000-03-14 | Crowley; Robert Joseph | Optical antenna array for harmonic generation, mixing and signal amplification |
| JP4537528B2 (en) * | 2000-03-29 | 2010-09-01 | 株式会社東芝 | Optical recording medium |
| JP2005099417A (en) * | 2003-09-25 | 2005-04-14 | Fuji Xerox Co Ltd | Optical switching device and optical device |
| EP1917557A4 (en) | 2005-08-24 | 2015-07-22 | Trustees Boston College | Apparatus and methods for solar energy conversion using nanoscale cometal structures |
| WO2007025023A2 (en) | 2005-08-24 | 2007-03-01 | The Trustees Of Boston College | Apparatus and methods for optical switching using nanoscale optics |
| US7623746B2 (en) | 2005-08-24 | 2009-11-24 | The Trustees Of Boston College | Nanoscale optical microscope |
| US7589880B2 (en) | 2005-08-24 | 2009-09-15 | The Trustees Of Boston College | Apparatus and methods for manipulating light using nanoscale cometal structures |
| WO2007086903A2 (en) | 2005-08-24 | 2007-08-02 | The Trustees Of Boston College | Apparatus and methods for solar energy conversion using nanocoax structures |
| EP2120569B1 (en) | 2007-01-12 | 2013-08-14 | Merck Sharp & Dohme Corp. | Spirochromanon derivatives |
| PE20081559A1 (en) | 2007-01-12 | 2008-11-20 | Merck & Co Inc | SPIROCHROMANONE DERIVATIVES SUBSTITUTED AS ACETYL COA CARBOXYLASE INHIBITORS |
| US8173045B2 (en) | 2008-05-28 | 2012-05-08 | University Of Washington | Diels-Alder crosslinkable dendritic nonlinear optic chromophores and polymer composites |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6019108A (en) * | 1983-07-13 | 1985-01-31 | Fujitsu Ltd | Production for optical guide |
| JPS63260854A (en) * | 1987-03-16 | 1988-10-27 | アメリカン テレフォン アンド テレグラフ カムパニー | Superconductor and manufacture |
| JPH01166555A (en) * | 1987-12-22 | 1989-06-30 | Canon Inc | Semiconductor element |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63220219A (en) * | 1987-03-10 | 1988-09-13 | Fujitsu Ltd | Electrooptic element and its production |
| US5045364A (en) * | 1990-05-18 | 1991-09-03 | At&T Bell Laboratories | Nonlinear optical devices and methods |
-
1989
- 1989-12-08 JP JP1317916A patent/JPH03182725A/en active Pending
-
1990
- 1990-12-07 DE DE69025564T patent/DE69025564T2/en not_active Expired - Fee Related
- 1990-12-07 EP EP90313351A patent/EP0431973B1/en not_active Expired - Lifetime
-
1992
- 1992-09-04 US US07/939,965 patent/US5547705A/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6019108A (en) * | 1983-07-13 | 1985-01-31 | Fujitsu Ltd | Production for optical guide |
| JPS63260854A (en) * | 1987-03-16 | 1988-10-27 | アメリカン テレフォン アンド テレグラフ カムパニー | Superconductor and manufacture |
| JPH01166555A (en) * | 1987-12-22 | 1989-06-30 | Canon Inc | Semiconductor element |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0431973A3 (en) | 1992-07-22 |
| US5547705A (en) | 1996-08-20 |
| DE69025564D1 (en) | 1996-04-04 |
| EP0431973A2 (en) | 1991-06-12 |
| EP0431973B1 (en) | 1996-02-28 |
| DE69025564T2 (en) | 1996-09-19 |
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